CN108101108B - β -Cu2V2O7Method for preparing powder - Google Patents

β -Cu2V2O7Method for preparing powder Download PDF

Info

Publication number
CN108101108B
CN108101108B CN201711342593.XA CN201711342593A CN108101108B CN 108101108 B CN108101108 B CN 108101108B CN 201711342593 A CN201711342593 A CN 201711342593A CN 108101108 B CN108101108 B CN 108101108B
Authority
CN
China
Prior art keywords
powder
preparation
precursor
crucible
placing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201711342593.XA
Other languages
Chinese (zh)
Other versions
CN108101108A (en
Inventor
曹丽云
王勇
黄剑锋
寇领江
李嘉胤
冯亮亮
赵亚娟
许占位
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shaanxi University of Science and Technology
Original Assignee
Shaanxi University of Science and Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shaanxi University of Science and Technology filed Critical Shaanxi University of Science and Technology
Priority to CN201711342593.XA priority Critical patent/CN108101108B/en
Publication of CN108101108A publication Critical patent/CN108101108A/en
Application granted granted Critical
Publication of CN108101108B publication Critical patent/CN108101108B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G31/00—Compounds of vanadium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Landscapes

  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

β -Cu2V2O7The preparation method of the powder comprises the following steps of (1-1.25): 1 weigh a defined amount of analytically pure V2O5And Cu2Placing O in a crucible, dropwise adding anhydrous ethanol to enable the powder to be ground for 1h in a wet state, and then adding V2O5And Cu2NH accounting for 2 to 5 percent of the total mass of O4And (4) continuing to grind (10-30) min, placing the grinded precursor in a crucible, heating to 640-750 ℃ from room temperature at the heating rate of 2 ℃/min, performing heat preservation reaction (1-10) h, and then cooling along with the furnace to obtain β -Cu for the anode of the lithium ion battery2V2O7The invention prepares β -Cu in a short time by a solid phase method2V2O7The preparation method of the powder is simple, the product purity is high, the crystallinity is good, cuprous oxide is used as a copper source, the preferential oxidation process of the cuprous oxide is utilized, the reaction time is shortened, ammonium chloride is used as a mineralizer, the gas phase mass transfer process is utilized, the reaction temperature is reduced, and the preparation method has the characteristics of short preparation period, simple process, high repeatability, strong feasibility, economy and practicability, and suitability for large-scale production and preparation.

Description

β -Cu2V2O7Method for preparing powder
Technical Field
The invention belongs to the technical field of electrode materials of batteries, and particularly relates to β -Cu for a lithium ion battery anode material2V2O7A method for preparing powder.
Background
Copper vanadate (Cu)xVyOz) Is a layered structure, and can perform multi-step reduction (Cu) during the process of lithium ion intercalation/deintercalation2+/Cu+And Cu+/Cu0) Is considered to be the lithium ion battery electrode material with potential application value β -Cu2V2O7The carbon nanotube is a monoclinic phase, and the C2/C space group has potential application values in the aspects of negative thermal expansibility, magnetism, catalytic oxidation and the like.
As a semiconductor material, β -Cu is currently used2V2O7The temperature required by synthesis is higher, and the reaction time is as long as 72 hours.
Disclosure of Invention
The invention aims to provide the-Cu with low synthesis temperature, short reaction time, simple and convenient operation and good safety2V2O7A method for preparing powder.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
1) the ratio of the amount of the copper-vanadium substance is (1-1.25): 1 analytically pure V2O5Powder and Cu2Placing O powder in a crucible, dropwise adding absolute ethyl alcohol, and grinding the powder under a wet state to obtain a mixture;
2) adding NH accounting for 2-5 percent of the mass of the mixture into the mixture4Continuing to grind Cl to obtain a precursor;
3) placing the ground precursor into a crucible, heating the precursor to 640-750 ℃ from room temperature at a heating rate of 2 ℃/min, carrying out heat preservation reaction, cooling the precursor along with a furnace after the reaction is finished, and obtaining β -Cu for the anode of the lithium ion battery2V2O7And (3) powder.
The grinding time in the step 2) is (10-30) min.
The heat preservation reaction time in the step 3) is (1-10) h.
The method has the beneficial effect that β -Cu is prepared in a short time by a solid phase method2V2O7The preparation method of the powder is simple, the product purity is high, and the crystallinity is good; and secondly, cuprous oxide is used as a copper source, and the reaction time is shortened by utilizing the preferential oxidation process of the cuprous oxide. Thirdly, adding ammonium chloride as a mineralizer, and reducing the reaction temperature by utilizing a gas phase mass transfer process. In conclusion, the method has the characteristics of short preparation period, simple process, high repeatability, strong feasibility, economy and practicability, and is suitable for large-scale production and preparation. The prepared product has sharp diffraction peak shape, good crystallinity and high purity. After the semi-cell is assembled for testing, the first discharge capacity is 357mAh/g, and the voltage platform is 2.5V. Can be applied to the anode material of the lithium ion battery.
Drawings
FIG. 1 shows β -Cu prepared by reacting for 2h at different temperatures according to the present invention2V2O7XRD pattern of the powder.
Detailed Description
Example 1:
1) according to the mass ratio of copper to vanadium of 1.25: 1 analytically pure V2O5Powder and Cu2Placing O powder in a crucible, dropwise adding absolute ethyl alcohol, and grinding the powder under a wet state to obtain a mixture;
2) adding NH accounting for 2 percent of the mass of the mixture into the mixture4Continuing to grind for 10min to obtain a precursor;
3) placing the grinded precursor in a crucible, heating the precursor from room temperature to 640 ℃ at a heating rate of 2 ℃/min, preserving heat, reacting for 10 hours, and cooling the precursor along with the furnace to obtain β -Cu for the anode of the lithium ion battery2V2O7And (3) powder.
Example 2:
1) according to the mass ratio of copper to vanadium of 1.15: 1 analytically pure V2O5Powder and Cu2Placing O powder in a crucible, dropwise adding absolute ethyl alcohol, and grinding the powder under a wet state to obtain a mixture;
2) adding NH accounting for 3 percent of the mass of the mixture into the mixture4Continuing to grind for 15min to obtain a precursor;
3) placing the grinded precursor in a crucible, heating to 680 ℃ from room temperature at a heating rate of 2 ℃/min, preserving heat, reacting for 5h, and cooling with the furnace to obtain β -Cu for the anode of the lithium ion battery2V2O7And (3) powder.
Example 3:
1) according to the weight ratio of copper to vanadium of 1: 1 analytically pure V2O5Powder and Cu2Placing O powder in a crucible, dropwise adding absolute ethyl alcohol, and grinding the powder under a wet state to obtain a mixture;
2) adding 4% NH of the mixture mass to the mixture4Continuing to grind for 20min to obtain a precursor;
3) placing the grinded precursor in a crucible, heating to 650 ℃ from room temperature at a heating rate of 2 ℃/min, keeping the temperature, reacting for 8h, and cooling along with the furnace to obtain β -Cu for the anode of the lithium ion battery2V2O7And (3) powder.
Example 4:
1) according to the weight ratio of copper to vanadium of 1: 1 analytically pure V2O5Powder and Cu2Placing O powder in a crucible, dropwise adding absolute ethyl alcohol, and grinding the powder under a wet state to obtain a mixture;
2) adding NH accounting for 5 percent of the mass of the mixture into the mixture4Continuing to grind for 30min to obtain a precursor;
3) placing the grinded precursor in a crucible, heating the precursor to 750 ℃ from room temperature at a heating rate of 2 ℃/min, preserving heat, reacting for 1h, and cooling along with the furnace to obtain β -Cu for the anode of the lithium ion battery2V2O7And (3) powder.
As can be seen from FIG. 1, the product has sharp diffraction peak, good crystallinity and high purity. After the semi-cell is assembled for testing, the first discharge capacity is 357mAh/g, and the voltage platform is 2.5V. Can be applied to the anode material of the lithium ion battery.

Claims (3)

1.β -Cu2V2O7The preparation method of the powder is characterized by comprising the following steps:
1) the ratio of the amount of the copper-vanadium substance is (1-1.25): 1 analytically pure V2O5Powder and Cu2Placing O powder in a crucible, dropwise adding absolute ethyl alcohol, and grinding the powder under a wet state to obtain a mixture;
2) adding NH accounting for 2-5 percent of the mass of the mixture into the mixture4Continuing to grind Cl to obtain a precursor;
3) placing the ground precursor into a crucible, heating the precursor to 640-750 ℃ from room temperature at a heating rate of 2 ℃/min, carrying out heat preservation reaction, cooling the precursor along with a furnace after the reaction is finished, and obtaining β -Cu for the anode of the lithium ion battery2V2O7And (3) powder.
2.β -Cu as set forth in claim 12V2O7The preparation method of the powder is characterized by comprising the following steps: the grinding time in the step 2) is 10-30 min.
3.β -Cu as set forth in claim 12V2O7The preparation method of the powder is characterized by comprising the following steps: the heat preservation reaction time in the step 3) is 1-10 h.
CN201711342593.XA 2017-12-14 2017-12-14 β -Cu2V2O7Method for preparing powder Active CN108101108B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201711342593.XA CN108101108B (en) 2017-12-14 2017-12-14 β -Cu2V2O7Method for preparing powder

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201711342593.XA CN108101108B (en) 2017-12-14 2017-12-14 β -Cu2V2O7Method for preparing powder

Publications (2)

Publication Number Publication Date
CN108101108A CN108101108A (en) 2018-06-01
CN108101108B true CN108101108B (en) 2020-02-21

Family

ID=62217025

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201711342593.XA Active CN108101108B (en) 2017-12-14 2017-12-14 β -Cu2V2O7Method for preparing powder

Country Status (1)

Country Link
CN (1) CN108101108B (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109301219A (en) * 2018-10-10 2019-02-01 郑州大学 A kind of lithium ion battery negative material and its preparation method and application
CN110482604B (en) * 2019-07-25 2022-01-25 广东工业大学 Cu2V2O7Nanorod potassium ion battery positive electrode material, potassium ion battery and preparation method thereof
CN114315351B (en) * 2022-01-24 2022-09-23 河南大学 High-entropy near-zero-expansion vanadate ceramic material and sintering synthesis method thereof
WO2023163058A1 (en) * 2022-02-28 2023-08-31 日本化学工業株式会社 Negative thermal expansion material, method for manufacturing same, and composite material
JP7427058B2 (en) 2022-02-28 2024-02-02 日本化学工業株式会社 Negative thermal expansion material, its manufacturing method and composite material

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105655582A (en) * 2016-02-05 2016-06-08 北京理工大学 Method for coating and modifying lithium vanadium phosphate positive pole material with novel carbon source
CN106099092A (en) * 2016-07-01 2016-11-09 陕西科技大学 A kind of preparation method of the copper vanadate for lithium ion battery negative material
CN106186062A (en) * 2016-07-01 2016-12-07 陕西科技大学 A kind of homogeneous hydro-thermal method prepares flower-shaped Cu2v2o7the method of material and the Cu of preparation2v2o7material

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105655582A (en) * 2016-02-05 2016-06-08 北京理工大学 Method for coating and modifying lithium vanadium phosphate positive pole material with novel carbon source
CN106099092A (en) * 2016-07-01 2016-11-09 陕西科技大学 A kind of preparation method of the copper vanadate for lithium ion battery negative material
CN106186062A (en) * 2016-07-01 2016-12-07 陕西科技大学 A kind of homogeneous hydro-thermal method prepares flower-shaped Cu2v2o7the method of material and the Cu of preparation2v2o7material

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Thermoanalytical study of the polymorphism and Melting Behavior of Cu2V2O7;B.V.Slobdin et al.;《Inorganic Materials》;20101231;第46卷(第2期);第196-200页 *
Unusually Large Magnetic Anisotropy in a CuO-Based Semiconductor Cu5V2O10;Zhangzhen He et al.;《J. Am. Chem. Soc》;20101230;第133卷;第1298-1300页 *
Zongliang Fan et al.;Preparation and Properties of Copper Vanadate Materials;《物理化学进展》;20150529;第4卷;第52-65页 *

Also Published As

Publication number Publication date
CN108101108A (en) 2018-06-01

Similar Documents

Publication Publication Date Title
CN108101108B (en) β -Cu2V2O7Method for preparing powder
CN101635349B (en) Method for preparing metal-silver-doped carbon-covering lithium iron phosphate of lithium-ion battery cathode material
CN111793824B (en) Surface-modified high-nickel cathode material and preparation method and application thereof
CN105932269B (en) The method that spray burning pyrolysis prepares anode material for lithium-ion batteries
CN106602060A (en) Low-cost lithium iron phosphate material, and preparation method and application thereof
CN110326136B (en) Novel high-potential multilayer carbon-coated polyanionic sodium-ion battery positive electrode material and preparation method thereof
CN104701538B (en) A kind of preparation method for lithium ion battery anode material lithium iron phosphate
CN103022490A (en) Method for preparing sodium fluorophosphate vanadium for positive pole material of sodium-ion battery
CN104752693A (en) Preparation method for lithium ion battery anode material lithium iron phosphate/graphene compound
CN106784748B (en) A kind of silicon substrate nickel cobalt manganese lithium ternary electrode material of lithium battery and preparation method thereof
CN106374104A (en) Method for preparing sodium fluorine vanadium phosphate material in air atmosphere
CN111115639A (en) Preparation of SiO by centering reactionxMethod and application of @ C material
CN110950315A (en) Preparation method of composite ion-doped lithium iron phosphate material
CN112777571A (en) Method for synthesizing battery-grade lithium sulfide
CN101944615A (en) Lithium-manganese phosphate anode material for lithium ion battery and preparation method thereof
CN106486658A (en) A kind of solid phase reaction prepares the method for silicon nano material and its application
CN110120503B (en) Composite cathode material and preparation method and application thereof
CN114105117A (en) Preparation method of precursor and nickel lithium iron phosphate cathode material
CN103159201A (en) High-pressure low-temperature preparation method for positive carbon-coated lithium iron phosphate composite material of lithium ion battery
CN103337607B (en) The method that lithium ferrosilicon silicate of lithium-ion battery cathode material is prepared by ilmenite
CN103579621A (en) Preparation method of battery positive material
CN108134058B (en) Cu5V2O10Preparation method of-CuO composite powder
CN110713187A (en) Preparation method of silicon material and application of silicon material in lithium ion battery cathode
CN110627114A (en) Modified lithium titanate negative electrode material and preparation method thereof
CN102856548B (en) Preparation method for lithium ferrous phosphate anode material coated by directly reduced nanocarbon

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant